Polymorph Engineering of TiO2: Demonstrating How Absolute Reference Potentials Are Determined by Local Coordination

Journal article

Buckeridge, J., Butler, K. T., Catlow, C. R. A., Logsdail, A. J., Scanlon, D. O., Shevlin, S. A., Woodley, S. M., Sokol, A. A. and Walsh, A. (2015). Polymorph Engineering of TiO2: Demonstrating How Absolute Reference Potentials Are Determined by Local Coordination. Chemistry of Materials. 27, pp. 3844-3851. https://doi.org/10.1021/acs.chemmater.5b00230
AuthorsBuckeridge, J., Butler, K. T., Catlow, C. R. A., Logsdail, A. J., Scanlon, D. O., Shevlin, S. A., Woodley, S. M., Sokol, A. A. and Walsh, A.
Abstract

We report that the valence and conduction band energies of TiO2 can be tuned over a 4 eV range by varying the local coordination environments of Ti and O. We examine the electronic structure of eight known polymorphs and align their ionization potential and electron affinity relative to an absolute energy reference, using an accurate multiscale quantum-chemical approach. For applications in photocatalysis, we identify the optimal combination of phases to enhance activity in the visible spectrum. The results provide a coherent explanation for a wide range of phenomena, including the performance of TiO2 as an anode material for Li-ion batteries, allow us to pinpoint hollandite TiO2 as a new candidate transparent conducting oxide, and serve as a guide to improving the efficiency of photo-electrochemical water splitting through polymorph engineering of TiO$_2$.

Year2015
JournalChemistry of Materials
Journal citation27, pp. 3844-3851
Digital Object Identifier (DOI)https://doi.org/10.1021/acs.chemmater.5b00230
Web address (URL)https://pubs.acs.org/doi/abs/10.1021/acs.chemmater.5b00230
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Print18 May 2015
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Accepted01 May 2015
Deposited24 Oct 2019
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Buckeridge et al. Reply:
Buckeridge, J., Catlow, C. R. A., Scanlon, D. O., Keal, T. W., Sherwood, P., Miskufova, M., Walsh, A., Woodley, S. M. and Sokol, A. A. (2015). Buckeridge et al. Reply: Physical Review Letters. 115 (2), p. 029702. https://doi.org/10.1103/PhysRevLett.115.029702
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